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Патент USA US2407492

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Sept- 10, 1946-
Filed June’ 11, 1945
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Patented Sept. 10, 1946
I 2,4e7,492
Larry G. .Hall, St. Louis, Mo., and. Herman G.
Boucher, Wood River, 111., assignors to Shell De
velopment Company, San Francisco, Calif., a
corporation of Delaware
Application June 11, 1945, SerialNo..598,708
7 Claims. (Cl. 196-50)
This invention relates to the ,productionof gas
material and considerable depreciation of‘ the
oline and especially aviation grade gasoline from
anti-knock properties of the gasoline. Re?ning
petroleums. More particularly the .invention re
by conventional acid treating followed by doctor
lates to a method of treatment whereby increased
treating and rerunning has the recognized dis
production of gasoline of any speci?ed quality 5 advantages of high acid consumption, poor-yields
and comprising. straightrungasoline and cracked
and depreciation of the anti-knock properties.
gasoline may be produced from a given amount of
In View .of these disadvantages such materials are
petroleum. in a more economical manner.
sometimes re?ned by catalytic methods referred
‘The primary aim of the. petroleum re?ner is to
to generally as hydro?ning. In this re?ning
produce the maximum amount of best quality 10 method'the material is treated under .hydrogen
gasoline .from a. given quantity of crude petroleum ' pressure in the presenceof asuitable hydrogena
tion catalyst. The chief advantage of hydro?n
in the most economical manner. Thus, the cri
terion of .the production obtained is not merely
ing over conventional acid re?ning methods is
the number of barrels of gasoline produced per
that the material may be refined with. less loss of
barrel of crude, nor the quality of the gasoline, 15 material. However, hydro?ning, as practiced at
present, is not Wholly satisfactory. The process
but a combination of these hereinafter referred
to as quality-barrel. The term "quality” in this
consumes considerable amounts of expensive hy
expression is a weighted numerical index of qual
drogen; furthermore, a considerable loss in anti
knock characteristics is usually caused by the sat
ity such as octane number or such other index as
may-be suitable. In general the quality of gaso 20 uration of at least part. of the ole?nic and/or
aromatic constituents of the gasoline.
line is ?xed by specification and the re?ner then
The re?ned cracked gasoline is then blended
strives to produce ‘the maximum amount of ma-,
with the maximum amount of the re?ned straight
terial .meeting such speci?cations.
run gasoline that can be tolerated while still
In ‘the usual practice the ?rst step in the pro
duction of gasoline from petroleum is to separate 25 maintaining the desired quality of the blend.
It will be appreciated that the re?nergusually
gasolinesconstituents naturally ‘occurring therein.
has at his disposal one or more additives such as
This is e?ected by a simple topping operation.
alkylate, isopentane, aromatic extract, cumene,
The product is known as straight run gasoline.
xylidine, tetraethyl lead, etc., which are usually
Straight rungasoline .consists essentially of sat
urated hydrocarbons and contains only small 30 added to the blend of cracked and straight run
gasoline to produce the ?nal gasoline product.
amounts of impurities which, due to their char
However, the amount of such additives that can
acter, are, jfurthermor'e, relatively easily removed.
be addedxto the blend .of cracked and straight run
It therefore _generally requires ‘and ' is given only
gasoline (sometimes referred to as base stock) is
a light acid re?ning treatment. .Straight‘run
gasoline, however, generally has very poor anti 35 limited by the limited availability of the'additives
or by speci?cations of such factors as heat con
knock characteristics :and is consequently of poor
tent, volatility, corrosiveness, and the like. The
minimum quality oi’ the blend of cracked and
straight run gasoline produced by the re?ner is
somewhatfurther into one or more-suchproducts 40 therefore usually below that of the ?nished gaso
line and is determined by‘ the amount of such ad
as-kerosene, naphtha, stove .oil, gas oil, and re
ditivesavailable .for use.
duced crude. One or more of .these products is
then cracked by various conventional cracking
In the process of the present invention straight
processes to produce additional amounts of gaso
run gasoline and cracked gasoline are produced
line. Any of the conventional cracking processes 45 from petroleum in the above described general
producing an ole?nic high anti-knock gasoline
manner. ‘The invention lies in the particular
product may be employed. However, in conven
'methodof handling these materials to produce
tional practice, catalytic cracking with clay-type
the ?nished blend. The cracked gasoline may
cracking catalysts is preferred since .such. proc
be produced from any portion of the petroleum
essesproduce gasoline of superior quality.
50 boiling above the gasoline desired and may be
The cracked gasolines contain appreciable
produced by any of the conventional cracking
amounts of sulfur ‘compounds, nitrogen com
and/or‘reforming methods which produce ahigh
pounds, diole?ns, acetylenic compounds, and
anti-knock ole?nic gasoline. A preferred method
other materials which are di?ioult to remove by
is, byythe catalytic cracking of petroleum oils
ord-lnaryire?ning methods without large losses of 55 with clay-type catalyst, Such ‘processes are, for
The material remaining after Ltopping to re
move straight run gasoline is usually separated
the order of 200-2000pounds per square inch are
illustrative. The hydrofining treatment may be
advantageously carried out at temperatures rang
ing from about 400° F. to about 10000 F. When
the material treated is high in sulfur (for exam
ple containing more than about 0.1%. sulfur) low
example, the Houdry process, the Thermofor
process, and the fluid catalyst catalytic cracking
process. The catalysts used in these processes
comprise certain selective natural clays and
earths, modi?ed clays, and various synthetic
clay-type catalysts. The clays are sometimes
used in their natural state but are usually treated
temperatures (below about 85()‘_) F.) consistent
with the activity of the catalyst and the other
and/or modi?ed for instance, by acid washing,
treating conditions are generally preferred.
removing iron-bearing impurities, leaching out- '
alumina, adjusting the ratio of silica to’ alumina,
and/or by incorporating minor amounts of pro
moters in order to increase their activity, stabil
ity, etc., or to reduce their carbon-forming tendl '
ency. Various synthetic clay-type cracking cata
lysts are also now widely used.
the material treated is low in sulfur (for exam
ple containing less than about 0.1% sulfur) high
er temperatures (for example, between about
850°F. and 1000°F;) may be preferred. The treat
ment afforded may be the minimum treatment
consistent with the desired degree of re?ning (as ‘
These catalysts
consist largely of silica and/oraluminaand/or
measured by the sulfur content, gum-forming
magnesia and are often modi?ed by minor
amounts of such materials as BzOs, AlFs, A1PO4,
ZI‘Oz, etc. Also certain promoters may be in
troduced along with the hydrocarbon stream en 20
effected with a minimum hydrogen consumption
and results in the minimum loss of anti-knock
properties. .In some cases, however, a more thor
tendency, etc); this allows the treatment to be
ough treatment to‘produce a substantially satu
tering the reaction zone. Such promoters in
clude boric oxide, hydro-gen, halides, organic hal
ides, etc. The speci?c catalyst forms no part of
the present invention and will not be described
in further detail.
rated product (particularly when operating at
the higher temperature levels) may be more ad
The separated cracked gasoline fraction con
sisting largely of Ce hydrocarbons is subjected
to a separate non-hydrogenating re?ning treat?
' In these processes the oil to be cracked is con
tacted, usually in the vapor phase, with the cat
alyst under suitable conditions of pressure and
residence time at a temperature usually‘ in the
order of 750° F. to 1200° F. depending upon the
treatment is carried out under ‘ conditions of
particular hydrocarbon feed, the particular cat
alyst, and the particular results desired.
acid concentration, temperature, time, etc., and
in the known manner to the extent necessary to
provide a suitable re?ning. The exact strength
and/or amount of acid required will depend to a
' According to the process of the present inven
tion there is separated from the cracked gasoline
prior to further handling an ole?nic fraction
consisting largely of Ceor C6-C7 hydrocarbons.
certain extent upon the amount of unsaturated
hydrocarbons present in the material treated and
Likewise there is separated from the straight run
gasoline prior to re?ning a substantially satu
to a certain extent upon the conditions employed
rated fraction consisting largely of Ce hydrocar
The separated straight run fraction is
blended with the remaining cracked gasoline.
Thus, the separated straight run fraction is sub
s'tituted for the separated cracked fraction in
the cracked gasoline. The two materials result
ing'are separately re?ned and then reblended. 45
In a preferred embodiment of the invention the
separated cracked fraction is also blended with
‘a remaining portion of the straight run gaso
line; thus the separated cracked fraction is also
‘substituted for the separated straight run frac~
tion in the straight run gasoline.
' The catalytic gasoline containing the separated
straight run fraction is mixed with a hydrogen
containing gas, and contacted with a hydrogena
tion ‘catalyst, i. e., hydro?ned,
‘and the blend'is subjected to the described re?né
ing treatment.
as a caustic solution.
This treatment may or
the desired end-point.
are the oxides and sul?des of V, Cr, Mn, Fe, Co, v
Particularly suitable catalysts '60
comprise a sul?de of a metal of the iron group,
preferably in combination with a sul?de of a
The hydro?ned blend and the acid treated
product are blended together in substantially
their entirety to produce the desired blend ' of
cracked gasoline and straight run gasoline (base
stock) having the necessary quality. To the base
stock blend there is usually then added various
‘metal of group VI of the periodic system of the
Examples of such preferred catalysts _
are nickel sul?de, iron sul?de, cobalt sul?de,
alone and in combination with sul?des of molyb
denum or tungsten. These catalysts may gen
amounts of one or more additives in accordance
"withtheir availability and with due regard to
‘specifications to produce the ?nal gasoline of the
erally bev used substantially continuously for
Although the novel features which’ are believed
to be characteristic of the process of the inven
tion are ‘mentioned above and are particularly
treatment is carried out in the presence of an
excess of hydrogen. The amount of hydrogen
employed is in general between about 1 and 30
pointed out in the claims appended hereto,_ the
mols per mol of hydrocarbon feed. (Only a por
tion of this hydrogen is consumed.)
sure may vary over a wide range. Pressures in
After acid treating the material is usually neu
tralized by washing with an alkaline reagent such
may not be followed by rerunning, i. e., cutting to
for this process. Examples of suitable catalysts
The pres-
The separated cracked gasoline fraction may,
in general, be more advantageously treated in a
blend with a remaining portion of the straight
‘run gasoline. Thus, according to a preferred
embodiment of the invention the separated
cracked fraction is blended with a. portion of the
.blendedwith' the remaining cracked gasoline)
The hydro?ning ‘ ,
hundreds of hours without regeneration.
used and since such methods are well known
there is no need to describe them in detail.
being the remaining tolerable straight run mate
rial above the separated straight run fraction
catalysts commonly employed and recommended
in the treating step. Any suitable method of
contacting the gasoline with the acid may be
remaining straight run gasoline (such portion
treatment may be carried out with any of the
Ni, M0 and W.
A preferred treatment is a conventional
acid re?ning treatment, for example, with sul
furic acid or spent alkylation acid (HzSOi). The
. .
process. ‘may. perhaps be better understood by
75 ‘referring to the‘ following'mor'e detailed descrip
tioneintwliichispeci?o preferred embodiments are
setforth. To assist in this description-reference
i’s“ had to thee-attached? drawing-wherein there is
shown» byeconventional \?'gures" a: simpli?ed2 flow
an: overheadiproduct-aa: cracked gasoline fraction
consisting; largely of? Ge: hydrocarbons: which‘. is
' removed‘lvia line/>31.“ The: stripped absorber oil
i'slrecycledit‘o theiabsorbe'rlvia. line 30.1
diagram of a‘: typi’cali applicationiof the’ process
stripping- column 3>61are1adjustedftoremoveas
The liquid hydrocarbon from . separators- 252' is
passed Via; liner- 385150. a - fractionatin'g‘ columns 392..
The‘ conditions in; fractionatin'g.v column; 39, are‘ 7
adjusted? to: remove;v as . air-‘overhead product 1 'sub‘»
Referring to the’ drawing; theefeed‘ent‘ering via
line 2l-is- topped
topping; column: I5 to= recover
overheadaelightrstraight run-fraction’ containing»
stantially: all ‘of the: materialiup through normal
hexane? This-overhead product removedlviakline'
4 Qii'sL passed to aisecondl- fractionating: columna 4"];
whereinzit isaseparated: into a‘: lower: boiling rfrace
tion»; consisting: of products! boiling’. up: through
normallpentaneiwh-iclr is: removed'cviazline 43 and
substantiallyall‘; of ' the C6’ hydrocarbons and if‘
desired-1 a“ portion’ of the; C’FHXdi'OCaI'B'OIIS; ' This
overheadfifraction-is ‘passed via= line 3-tb fraction
atin‘gr column 4'5v wherein-i it» is separated? int'o»a
l'ow‘er'b'oi-ling overheadl fraction containing’ subf
stant'ially'all' of-‘theconstituentsup through» pen
taneW-hichi's'withdraWn via line 45,1- andi a higher
boiling "fractione consistingflargely' of ‘theéstrai'ght
aehigher'boiling fraction; consisting. large-13b 0131616
hydrocarhonsawhich is removedtvialine?; This ‘
(3s .fra‘c-ti‘oniis :combin'ed : with the 1 crackediCs; fraca
run‘ (‘it hydrocarbons‘ which is withdrawn’ via
line 6% The‘lower boiling*ma’terial'fwitlidrawn‘via
tioni removed from: the > stripper? 35 via; line; 3:1;
ized cracked gasoline as hereinafter described:v .'
,- Thdcrackedigasoline fromwl'ii'chthe?Cs hydro:
carboni fraction: has: been) ‘removed, is; withdrawn
from fractionating columnist): via line 44; This
material; may: be; out? to; a: desired end-point in
line/ 5} may be-vtreatedi andi/orj utilized in any die-‘ 20 The: combined fractions; are; blendect with: the
straight: run- material; and separately: treated; as
sired‘ manner. The: straight I run; fraction with
hereinafter described-s
drawn vial line’ 6-1is=combined with the» d‘eliexan
Thez toppedi feediremovedf from column‘ I5 via
line T is- passed‘ to- a," fractionatin'g column 8
wherein» a/further -' portion‘ of straight? runligaso
fractionatingmolumn 451. The overhead product
line-is separated? The. amount of straightrun
from: fractionator? 4'51- withdrawn ,viailinei 46; iSEthB
crac-lsed:v gasoline; fractiom from. which the: Cathy;
gasoline separated‘ and‘ removedloverhead‘ v-iarline
9 is preferably adjusted with respecttuthemax
imum tolerable amountotstraight run gasoline
tobe included in the ?nished gasoline. Thus,
for example, in a typical operation the material
removedifrom fractionating~column 8 via 1ine 9
may- heme an- endepoint ~of, for. instance 185i’ E.
This material vis combined; with the.- cracked. C‘s 35
fraction as‘ hereinafterdescrib'edi
drocarbonshavesbeenzsubstantially remoyedsn The
Ca; hydrocarbom fraction removed; from the
crackedrgasoline as hereinbeforeadescribediisisuba
stitutefd? on'replace'd; by: the: straight: run fraction
separated: ‘as; hereinbefore: described‘... ‘Bhusg, the
straightrun: fractionawithdrawrr, from: fractionate
ing. column ; 4: viazlinet» 6., is; blended; with; the ; CV81‘?
head; product: from: fractionating; column 45.
The bottom product" irom f‘ractionazton 81?. is
passed via 1ine~ Hi-toa furtherefractionatingrcol;
This blend: is; mixedi with: an ; excess of: hydrogen
(with respect to that required;f0r;:~complete;sate
umn H to remove additio‘nalg'materialisuch: as
naphthankerosene, or the. like. Such“ materials 40 uration‘: of: thergasolinel' entering'via‘line 41.; For
example; the, amountazof' hydrogen: introduced ~I Via
areremoved overheadvialine l2 and may be
line~ It?" may bGLG? molsvper mol of hydrocarbon
treatedand/o'r used in anydesired?manner. The
Tliexmixture preheated.‘ to: a suitable‘; re
higher,boilingresiduefrom fractionator. H" (re
action; temperatures (for example-850? F2) in ‘a
duced crude)? is passed‘vialinessw' and‘ If to a
suitable- preheat‘en' 48'.- and:' passedtto catalytic: re
suitable heater l5'and tar separator‘ l6. Heavy
actor: 49.». Reactor 49 contains acsuitablerhydroe
residue or ‘taro is removedpvia line I'L vaporized
g'enatiorr-dehydrogenationz catalyst~~ such, __ for.‘ ex
material'i'stllenpassed'via, line l8 ‘to a cracking
ample; as; at pelleted :7 mixture‘ of nickel: sul?de
reactor, [9? wherein it is cracked in theconven
tungsterr sul?de; The‘ conditions/of,‘ pressure. and
tional‘manner. with one ofithe conventional clay
contactrtimeamay be. adjusted: to. effect. a: sub
t‘ypei cracking,‘ catalysts, The; cracked‘ product
stantiall‘v:v complete hydrogenation of the. ole?ns.
leaves 'thelcracking reactor via line‘ 20‘ and passes
Under such: conditions; the": sulfur; compounds
to a, ?'actionatingwcolumn' 2'!‘ wherein the con
and/or:- nitrogerr compounds: will' be; 1argely,»re.
vertedllproducts are separated from‘ unconverted
moved or: decomposed: and; a1so= dehydrogenation
and'insuf?cientl'y. converted material; This'late
ofinaphthenicz» constituents of: .theefeed may; take
t'er. material may be withdrawn Via‘ line" 22"v or
place. Typical conditions; are,‘ for example; a
‘recyclediin Whole or in. part‘ Vi'a. line; 13‘ to" the
aboutz850 p.- s. ihandeatliquid hourly
cracking reactor.
space velocity of‘. about 4. The productwithdrawn
sistingessentially of gasoline and‘ gases passes
viaelineillrv is passed to a‘conventional separating
over-lieadfrom fractionator" 21' viailine' 24 to a
cooler 25 and‘separator. 2B‘;
The 'vaporous product from separator 26 is
withdrawn via linet2'l», compressed by compressor
28, and passed to a typical adsorption system.
Thus», this vaporous product" is contacted under
'pressurelini absorber'2‘9 with a suitable naphtha
in..the drawing by a single separator 5|. Gas rich
inhydrogeniswithdrawn from the; separator 5|
and recycled via pump 52" and line 41. Inv order
to maintain a suitable concentration of‘hydrogen
or=oil1 fraction recirculated’ via" line 38‘. Dry: gas
'in‘ther recycle" gas some of this’ gas'may'be with
drawn? from‘ the‘ system‘ via line 53' and‘ make-up
is' removedfrom'the absorbers-via line*3l., The
absorber liquid‘ containing: the absorbed; hydro;
' hydrogen may beadded‘ via-‘lineiil. The hydro
?ned: blend- of ‘ crackedi and‘ straight run gasoline
withdrawn from separator 5| via‘line '5 S'isblended
33?. The‘conditions:instrippin'gg-column 33; are 70 with theacid‘ treated blend or straight‘ run gaso
line and" cracked’ gasoline as hereinafter described
adjusted’ to=remove as'an overhead product sub‘
and treated? by suitable means‘ to: remove hydro
stantially all "of they absorbed‘ material up through
gen' sul?de“ formed in' the- hydro?ning ‘treatment.
normal pentane; which‘ product is removed’ via
Thus, the hydro?nedi gasoline is :mixed with causa
line 341. The. absorber- oilithen- passes via'line 35
to a further stripping'co‘lumn-36. ,Tlieconditions 75 ti’c'» solution= entering-1- viaeline- 56: and. passed tm a
carbon-s’ passes via line 32>; to a: stripping column
caustic treater 51.‘ The product is withdrawn to
is a very desirable and most advantageous method
a settler 58. Caustic solution is recycled via line
The principal advantage of the process of the
56. Make-up caustic is added via line 59.
invention is that it allows the production of gaso
The straight ,run gasoline from which the C6
line of any speci?ed quality (in which a blend
hydrocarbons, and if desired also some of the C7
of straight run gasoline and cracked gasoline
hydrocarbons, have been removed as hereinbe
can be used-and this is in nearly every case) to
fore described (withdrawn from fractionating col
be appreciably increased without increasing the
umn 8 via line 9) is blended with‘the combined
catalytic Cs fractions separated as hereinbefore
hydrogen requirement. Thus, for example, in a
de?ned (entering via lines 3'! and 42). This blend 10 typical plant producing, for instance, about 9,000
B./D. of aviation base stock with a consumption
passes via line 31 to an acid treater 60 wherein
of 1.57 million cubic feet hydrogen the produc
it is contacted with sulfuric acid, spent alkyla
tion may be increased between about 100 and 400
tion acid, or other suitable acid under conditions
B./D. In many instances the increased produc
chosen with respect to the particular feed to af
ford the degree of re?ning required for the par 15 tion may also be obtained with decreased oper
ticular gasoline being produced. In the produc
ating expenses.
tion of automotive gasoline, for example, a very
volume production is not desired the advantage
mild re?ning treatment at low temperature and
with relatively dilute acid may be su?‘icient. In
of the process of the invention may be realized
either in the production of an equal volume of
gasoline of improved quality or in the produc
tion of an equal volume of gasoline of equal qual
ity with decreased consumption of more costly
The advantage of the described method of oper
the production of certain types of aviation gaso
line, on the other hand, a relatively severe treat
ment with a more concentrated acid may be re
quired. The acid treated material is withdrawn
to a separator Bl. Acid is recycled via line 62.
Make-up acid is added via line 63. The acid
treated material is withdrawn from the separator
via line 64. This material is combined with the
If for some reason increased
ation in a typical case is illustrated in the fol
lowing example in which it is assumed that a
re?ner with the following materials available de—
sires to produce the maximum amount of ANF-28
hydro?ned blend of cracked and straight run ma
aviation gasoline:
terial from line 55 and is neutralized in the caus
tic scrubber 51. The ?nished blend or base stock 30
Example I
consisting of straight run gasoline and cracked
gasoline properly re?ned and in the desired pro
portions is withdrawn via line 65. In general a
portion of the cracked C5 fraction is included in
the ?nished gasoline. This material requires a
caustic treatment to remove mercaptans and hy
drogen sul?de. This material, withdrawn via line
Depentanized straight run base stock...
B _/D_
4, 000
Catalytic cracked depentanized base sto
Catalytic cracked C5 fraction _________ __
Isopentane (95%) ____________________________________ __
Debutanized C4-C5 alkylate
6, 450
34, may be blended with the gasoline entering
umene __________________________________________ __
l, 000
the caustic treater.
Hydrogen (million cubic feet) ______________________ _.
l. 57
It will be appreciated that the system described 40
above and illustrated in the drawing is merely a
In normal operation (case 1) 4000 B./D.'of
typical example of the process of the invention
depentanized catalytic cracked base stock is hy
and may be modi?ed in various particulars. For
dro?ned, 1000 'B./D. of depentanized catalytically
example, the hydro?ned blend and the acid treat
ed blend may be caustic treated separately and ‘3 cracked base stock is acid treated, 1621 B./D.
of depentanized straight run base stock is acid
each or both of them may be cut to the desired
treated. The products are then blended. The
gasoline end-point (rerun) prior to the ?nal
maximum production of ANF-28 aviation gaso
blending. Also, for example, in actual practice
line is 15,265 B./D. When operating according to
the separation and recovery system illustrated by
the process of the invention (case 2) the cata
the simple separator 5! may be complicated by '
a system for removing hydrogen sul?de from the
lytically cracked Cs fraction andthe straight run
recycled hydrogen stream and/ or by the utiliza
tion of multiple compression and cooling steps.
Also, the combinations of fractionating equip
of 4,500 B./D. of dehexanized catalytically
cracked base stock and 1,000 B./D. of the straight
ment and method of handling to recover and sep
arate the speci?ed fractions may be altered With
out departing from the spirit of the invention. It
is not essential that the cracked gasoline and
Cs fraction are exchanged as described. A blend
run hexane fraction is hydro?ned.
A blend of
254 B./D. of catalytically cracked C's fraction and
1,150 B./D. of hexanized straight run base stock
is acid treated. The materials are then blended.
The maximum production of ANF-28 aviation
straight run gasoline be derived from the same
60 gasoline is 15,625 l3./D. Thus, case 2 affords an
petroleum. The straight run fraction, for exam
increased production of 360 B./D.
ple, may be derived from any, preferably naph
Example II
thenic, petroleum while the cracked gasoline may
be derived from the cracking or reforming of
Petroleum was topped to- recover a straight run
any'feed stock. Also, the separation of the re 65 gasoline fraction and various intermediates.
spective Cs fractions may be altered or adjusted
Catalytically cracked gasoline was produced from
to afford the optimum production of gasoline ac
various heavy petroleum products by the ?uid
cording to the circumstances. For example, the
catalyst cracking process using the present com
straight run fraction containing C's hydrocarbons
mercial silica-alumina composite cracking cata
may be cut to include a considerable portion of
C7 hydrocarbons and may be cut in such a man
ner as to be relatively concentrated in Cs and C7
naphthenes. When the straight run gasoline con
tains appreciable amounts of naphthenic hydro_
lyst. The straight run gasoline was fractionated
to recover separately a fraction consisting essen
tially of Ce hydrocarbons and then rerun to an
end-point of about 185° F. The catalytically
cracked product was treated to recover catalyti
.carbons (and most straight run gasolines do) this 75 cally cracked C5 hydrocarbons and catalytically
cracked Cc hydrocarbons separately and topped
arating from a cracked gasoline an ole?nic frac
tion consisting largely of C6 hydrocarbons, replac
to produce a dehexanized catalytically cracked
gasoline having an end-point of about 325° F.
ing said separated ole?nic fraction with a satu
rated straight run gasoline fraction concentrat
ed in C6 and C7 naphthenes, subjecting the thus
produced blend of said dehexanized cracked gaso
The dehexanized catalytically cracked gasoline
was blended with the straight run C6 fraction to
produce a feed blend having the following prop
line and straight run gasoline fraction to a hy
dro?ning treatment under hydrogen pressure in
the presence of a hydrogenation catalyst, sub
10 jecting said separated ole?nic fraction to an acid
Gravity, API _________________ ..
ASTM distillati
IBP . . . . _ . . . _
55. 5
50. 6
_ _ _ __
re?ning treatment, and recombining the acid re
?ned material with the hydro?ned blend.
_. ___ _ _
E. P
Sulfur, % w_____
Unsaturates, % w . _ _ _ . _
Aromatics, % w ______ __
BON, + 4.6 cc. TEL-__
Index N0. + 4.6 cc. TE
315 15
_ _ _ ._
_ 3. In the production from petroleum of gasoline
comprising straight run gasoline and cracked gas
38. 5
5. 8
30. 4
________ __
________ __
34. 5
This blend was hydro?ned with a nickel sul?de
tungsten sul?de catalyst under the following ap
proximate conditions:
Temperature ______________________ __°F__ 900
Pressure _________________ ___ ____ ._-p. s. i__ 840
Liquid hourly space velocity _____________ __
-Mol ratio of hydrogen to hydrocarbon____; 6:1
oline, the improvement which comprises separat
ing from a cracked gasoline an ole?nic fraction
consisting largely of Ce hydrocarbons, separating
from straight run gasoline a saturated fraction
consisting largely of Ce hydrocarbons, blending
20 said latter fraction with the remainder of the
cracked gasoline, subjecting the blend to a hy
dro?ning treatment under hydrogen pressure in
the presence of a hydrogenation catalyst, blend
, ing said ole?nic fraction separated from the
cracked gasoline with the remainder of the
straight run gasoline, subjecting this latter blend
to an acid re?ning treatment, and blending the
two thus-treated gasolines.
The product had the properties speci?ed in the
above table. The catalytically cracked fraction
consisting essentially of Ce hydrocarbons was
blended with the straight run gasoline remaining
after the separationof the C6 fraction. This
4.7In the production from petroleum of gaso
line comprising straight run gasoline and cracked
gasoline, the improvement which comprises sep
arating from a cracked gasoline an ole?nic frac
tion consisting largely of C6 hydrocarbons, sep
arating from straight run gasoline a saturated
fraction relatively concentrated in C6 and C7
blend was treated with about 20 pounds per bar
rel of spent alkylation acid, caustic washed and
rerun. The losses were about 18%. The acid
treated blend was then blended with the hydro
?ned blend to produce the final blend or base
naphthenes, blending said latter fraction with the
remainder of the cracked gasoline, subjecting the
blend to a hydro?ning treatment under hydrogen
pressure in the. presence of a hydrogenation cat
We claim as our invention:
1. In the production from petroleum of gaso
line comprising straight run gasoline and cracked
gasoline, the improvement which comprises sep
arating from a cracked gasoline an ole?nic frac
tion consisting largely of Ce hydrocarbons, replac
ing said separated ole?nic fraction with a satu
alyst, blending said ole?nic fraction separated
from the cracked gasoline with the remainder of
.the straight'run gasoline, subjecting this latter
blend to an acid re?ning treatment, and blend
ing the two thus-treated gasolines.
5. Process according to claim 1 in which the
cracked gasoline is a catalytically cracked gaso
rated straight run gasoline fraction consisting
lineobtained by cracking a hydrocarbon oil with
largely of C6 and C7 hydrocarbons, subjecting the
a clay type cracking catalyst.
. .
thus produced blend of said dehexanized cracked
6. Process according to claim 1 in which the
gasoline and straight run gasoline fraction to a 50 hydro?ning treatment is carried out with a hy
hydro?ning treatment under hydrogen pressure
drogenating metal sul?de catalyst. at a tempera
in the presence of a hydrogenation catalyst, sub
ture of about 850° F. and 1000° F.
jecting said separated ole?nic fraction to an acid
7. Process according to claim 1 in which the
re?ning treatment, and recombining the acid re
acid re?ning treatment is carried out under mild
?ned material with the hydro?ned blend.
conditions to leave the major portion of the ole
2. In the production from petroleum of gaso- I
?ne intact.
line comprising straight run gasoline and cracked
V .
gasoline, the improvement which comprises sep
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